Organic semiconducting compositions and N-type semiconductor devices

Abstract

An organic semiconducting composition consists essentially of an N,N-dicycloalkyl-substituted naphthalene diimide and a polymer additive comprising an insulating or semiconducting polymer having a permittivity at 1000 Hz of at least 1.5 and up to and including 5. This composition can be used to provide a semiconducting layer in a thin-film transistor that can be incorporated into a variety of electronic devices.

1. An organic semiconducting composition consisting essentially of an N,N-dicycloalkyl-substituted naphthalene diimide and a polymer additive comprising an insulating or semiconducting polymer having a permittivity at 1000 Hz of at least 1.5 and up to and including 5, wherein the organic semiconducting composition is capable of exhibiting a field electron mobility greater than 0.001 cm 2 /V·sec,
 the polymer additive has a permittivity at 1000 Hz of from 2 to 4, at least 95 weight % of its atoms are hydrogen, fluorine, and carbon atoms, and is a styrenic polymer, polyalkylene, poly(meth)acrylate, polyalkene, polynaphthalene, polycycloalkyl, or combinations thereof, and the polymer additive is present in an amount of at least 5 and up to and including 50 weight %, based on total organic conducting composition weight, and 
 the naphthalene diimide is represented by any of the following Structures (IIIa), (IIIb), (IVa), and (IVb): 
 
       
         
           
           
               
               
           
         
       
       wherein R 4  is a C 1 -C 12  alkyl group, C 2 -C 8  alkylene group, substituted phenyl or cyclohexyl group, C 1 -C 8  alkoxy group, C 1 -C 8  carbonyl, carboxy substituent, carbonyl-containing substituent, fluorine, or fluorine containing organic or inorganic group, R 8  is H, any of the substituents defined for R 4 , or an N,N′-cycloalkyl-substituted naphthalene-1,4,5,8-bis-carboximide moiety in which one of the imide nitrogen groups in the R 8  group is the point of attachment to the cyclohexyl group either directly or indirectly to provide a bis compounds based on a central moiety that is disubstituted with two N,N′-cycloalkyl-substituted naphthalene-1,4,5,8-bis-carboximide moieties, the Y groups are independently alkyl, alkenyl, alkoxy, aryl, or arylalkyl groups, halogens, cyano, fluorine-containing groups, carbonyl-containing or carboxy-containing groups, and m is an integer of from 0 to 2, and
 the naphthalene diimide is present in an amount of at least 50 and up to and including 95 weight %, based on the total organic semiconducting composition weight. 
 
     
     
       2. The composition of  claim 1  wherein the polymer additive comprises one or more of the following polymers having the listed low frequency (1000 Hz) permittivity: 
       
         
           
                 
                 
                 
               
                     
                 
                     
                   Polystyrene 
                   2.5 
                 
                     
                   Poly(α-methylstyrene) 
                   2.6 
                 
                     
                   Poly(α-vinyl naphthalene) 
                   2.6 
                 
                     
                   Poly(vinyl toluene) 
                   2.6 
                 
                     
                   Polyethylene 
                   2.2-2.3 
                 
                     
                   cis-Polybutadiene 
                   2.0 
                 
                     
                   Polypropylene 
                   2.2 
                 
                     
                   Polyisoprene 
                   2.3 
                 
                     
                   Poly(4-methyl-1-pentene) 
                   2.1 
                 
                     
                   Poly(4-methylstyrene) 
                   2.7 
                 
                     
                   Poly(chorotrifluoroethylene) 
                   2.3-2.8 
                 
                     
                   Poly(2-methyl-1,3-butadiene) 
                   2.4 
                 
                     
                   Poly(p-xylylene) 
                   2.6 
                 
                     
                   Poly(α-α-α′-α′ tetrafluoro-p-xylylene) 
                   2.4 
                 
                     
                   Poly[1,1-(2-methyl propane)bis(4- 
                   2.3 
                 
                     
                   phenyl)carbonate] 
                     
                 
                     
                   Poly(cyclohexyl methacrylate) 
                   2.5 
                 
                     
                   Poly(chlorostyrene) 
                   2.6 
                 
                     
                   Poly(2,6-dimethyl-1,4-phenylene ether) 
                   2.6 
                 
                     
                   Polyisobutylene 
                   2.2 
                 
                     
                   Poly(vinyl cyclohexane) 
                   2.2 
                 
                     
                   Poly(vinyl cinnamate) 
                   2.9 
                 
                     
                   Poly(4-vinyl biphenyl) 
                   2.7 
                 
                     
                   Poly(methyl methacrylate) 
                       3.1-3.5. 
                 
                     
                 
             
                
               
               
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
       3. The composition of  claim 1  wherein the naphthalene diimide have a lowest unoccupied molecular orbital energy level of from about 3.5 eV to about 4.6 eV with reference to the vacuum energy level. 
     
     
       4. The composition of  claim 1  wherein the naphthalene diimide is present in an amount of at least 75 and up to and including 95 weight %, based on the total composition solids. 
     
     
       5. A thin-film, field-effect transistor comprising a dielectric layer, a gate electrode, a source electrode, a thin film of an organic semiconducting composition of  claim 1 , and a drain electrode,
 wherein the dielectric layer, the gate electrode, the thin film of organic semiconductor material, source electrode, and the drain electrode are in any sequence as long as the gate electrode and thin film of the organic semiconducting composition both contact the dielectric layer, and the source electrode and the drain electrode both contact the thin film of the organic semiconducting composition. 
 
     
     
       6. The transistor of  claim 5  wherein the thin film of the organic semiconducting composition is capable of exhibiting a field electron mobility greater than 0.1 cm 2 /V·sec. 
     
     
       7. The transistor of  claim 5  that has an on/off ratio of a source/drain current of at least 10 4 . 
     
     
       8. The transistor of  claim 5  wherein the gate electrode is adapted for controlling, by means of a voltage applied to the gate electrode, a current between the source and drain electrodes through the thin film of organic semiconductor material. 
     
     
       9. The transistor of  claim 5  wherein the source, drain, and gate electrodes each independently comprise a material selected from doped silicon, metal, and a conducting polymer. 
     
     
       10. An electronic device selected from the group consisting of integrated circuits, active-matrix display, and solar cells comprising a multiplicity of thin-film transistors according to  claim 5 . 
     
     
       11. The electronic device of  claim 10  wherein the multiplicity of the thin-film transistors is on a non-participating support that is optionally flexible. 
     
     
       12. An article comprising a support having disposed thereon a dry organic semiconducting layer consisting essentially of an N,N-dicycloalkyl-substituted naphthalene diimide and a polymer additive comprising an insulating or semiconducting polymer,
 wherein the organic semiconducting layer is capable of exhibiting a field electron mobility greater than 0.001 cm 2 /V·sec, 
 the polymer additive has a permittivity at 1000 Hz of from 2 to 4, at least 95 weight % of its atoms are hydrogen, fluorine, and carbon atoms, and is a styrenic polymer, polyalkylene, poly(meth)acrylate, polyalkene, polynaphthalene, polycycloalkyl, or combinations thereof, and the polymer additive is present in an amount of at least 5 and up to and including 25 weight %, based on total layer weight, and 
 the naphthalene diimide is represented by any of the following Structures (Ma), (IIIb), (IVa), and (IVb): 
 
       
         
           
           
               
               
           
         
       
       wherein R 4  is a C 1 -C 12  alkyl group, C 2 -C 8  alkylene group, substituted phenyl or cyclohexyl group, C 1 -C 8  alkoxy group, C 1 -C 8  carbonyl, carboxy substituent, carbonyl-containing substituent, fluorine, or fluorine containing organic or inorganic group, R 8  is H, any of the substituents defined for R 4 , or an N,N′-cycloalkyl-substituted naphthalene-1,4,5,8-bis-carboximide moiety in which one of the imide nitrogen groups in the R 8  group is the point of attachment to the cyclohexyl group either directly or indirectly to provide a bis compounds based on a central moiety that is disubstituted with two N,N′-cycloalkyl-substituted naphthalene-1,4,5,8-bis-carboximide moieties, the Y groups are independently alkyl, alkenyl, alkoxy, aryl, or arylalkyl groups, halogens, cyano, fluorine-containing groups, carbonyl-containing or carboxy-containing groups, and m is an integer of from 0 to 2, and
 the naphthalene diimide is present in an amount of at least 75 and up to and including 95 weight %, based on the total layer weight.